Extraction of hydrocarbon products from shales and coal.



D. T. DAY. EX-TRACTION OF- HYDHOCARBON PRODUCTS FROM SHALE AND COAL.

APPLICATION FILED SEPT-28. 1917.

Patented Dot. 1, 1918.

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UNITED sTATEs PATENT orrici.

DAVID T. DAY, or WASHINGTON, DISTRICT OF COLUMBIA, AssIeNOR Tovnmmsnfz. REED, or DENVER, COLOnADO.

EXTRAOTION OF IIYDnOOAnBON PRODUCTS FROM sIIALEs AND COAL.

Specification of Letters Patent.

Application filed September 28, 1917. Serial N O. 193,743.

To aZZwwm t may concern.' Be it known that I, IQAvIoT. DAY, a citizen of theUnited States, reslding at Washington, in the District of Columbia, have invented new and useful Improvements 1n the Extraction of Hydrocarbon Products from Shales and Coals, of which the following is a speciiication. l

This invention relates to improvements '10 in the extraction of hydrocarbon products,

nitrogen bases, oils and the like from shales and coals.

One feature of the invention relates to the combined extraction of material by solvent action and destructive distillation, the process being conducted in the presence of an acid added or obtained by distillation.

A further feature of the invention includes the use of vapors derived from the shale as a novel solvent for the volatile matter present in such shale or coal.

In the ordinary process of obtaining oils and other hydrocarbon products, nitrogen bases, and the like, from shales, and in some cases from coals, it is customary to heat these shales in stills without access of air. Usually vertical stills are employed, the shale being introduced at the top, and after its introduction, the top is closed with a ball hopper or other device. Heat is applied the bottom of the still for thepurpose of breaking up highlyr'esilient compounds, and especially -in increasing the formationof ammonia as a valuable by-product. In other cases, screw or endless chain conveyers 40 are used for carrying the shale through hot tubes, the vapors being taken oli' at the upper or lower end of the heated tube. In each instance the profit in operating such a still increases with the amount of volatile material which can be driven olf from the shale, and on the other hand the profit ceaseswhen the shales yield such a small proportion of oils, and the like, that they yield less in value than the combined comparatively high cost of heating the body of shale and cost of furnishing heat for the evaporation of the volatile matter. The heat re` vquired is greater than in the distillation of oils, for beside the quantity consumed in the distillation of alread existing oil in the shale is that heat needed7 for the'high tem- "perature required for the destructive disti1- lation Of the organic matter in the shale.

It is well known that many shales contain considerable oil already existing as oil, which is shown by the fact that this can be extracted by suitable solvents such as ether,

benzol and other light aromatic oils, gaso' Iene, phenol, etc. In some cases I have obtamed as much as three ifths of the oil obtainable by distillation, tion with a hot solvent. based merely on extraction by solvents would be costly, and would also leave valuable volatile products still ypresent in the-shale,

especially nitrogen ybases and other com-V poundsobtainable by destructive distillation. It is the aim, therefore, of the present process, to combine extraction by solvents with destructive distillation with the effect of recovering as great a percentage as possible of the solvents at a low temperature and ,leave as little work as possible to be etfected'by destructive distillation at high temperatures, and therefore at high cost.

In this process a certain ount of the Patented ct. il, i918.,

by simple extrac- A process, however,

volatile matter by the action of shale is iirst introduced from the extraction chamber described hereafter into an -in clined, tubular retort, which is then subj ected tothe temperature necessary tordrive out all of the volatile matter. This volatile v'matter is then delivered in the form of vapor, or vapor and'liquid, into an extrac-l` tion chamber containing the shale to be.

heated. These vapors condense to a certain extent in the chamber of cold shale and the hot condensed liquids exert the maximum solvent action possible and thereby take out of the shale a large proportionof the contained volatile materials. Some of the vapor in passing through the shale will enter the pores of the shale and combine with the oil therein rendering this oil thinner and give it a tendency to flow out of the shale. The resulting liquid is drawn off at'the bottom of this chamber and the shale, thus partially deprived of its volatile matter 'and liquid, is delivered through the bottom of the-shaleholding chamber on to a screw or other conveyer by which it is delivered into the first mentioned hot tube or retort where the remaining'vola-tile matter is extracted by de "from the shale itself as anew solvent for the 4structive distillation. Theresultin'g vapors J are-'continually delivered into the .shale or container., As aresult, the necessary amount lof expensive work of destructive distillation is reduced in proportion to the percentage t e of 'the soluble constituent taken from l shale.

This process presents the useof the vapors volatile matter in lsuch shale. It has'been 'found that much of the hydrocarbon mate# rial present in shales is adsorbed `to the surface of the shale particles and permeates the shale-in sucha way as to be insoluble until acted upon by acid or basic substances such as phenol, pyroligenous acids, pyr1d1ns,and acid or basic substances, when thc volatlle matter becomes' soluble in benzol or other aromatic hydrocarbons or gasolene containing phenols. The present process ellminates much expensive treatment by providing for the use of said solvents found directly in the condensed vapors from the shale itself. The

1 invention also provides the use of acids, in-

cluding mineral acids, as solvents, without regard to theirorigin, and thel invention is not limited to their formation by distillation from the shale.

In the operation of the invention, the process may be carried out by means of the apparatus illustrated in the accompanying drawing in which 1 indicates an extraction chamber in which fresh cold shale is subjected to the'solvent action of vapors as will be further'des'cribed. Located above the chamlber 1 is aI receivin hopper 2 arranged to receivematerial suc as shale or coal brought thereto by means of suitable conveyer apparatus indicated by 3. It is advantageous to crush the ore, shale or coal, and allow 1t to dry as much as possible before treating it with solvents. While the shale or other -'similar material is on the conveyer or in the receiving hopper '2, or -whlle it vis in the chamber l, it receives from the pipe 2 a very fine spray of acidulated water or dilute acid,

either hydrochloric or sulfuric acid, or any vpart of shales or other porous substances.

The invent-ion consists in the discovery that this bond 'is easily broken up by a dilute acid in which apparently the acid is not used up to any perceptible extent, and does not enter into chemical combination withv the oil. At the same time that this fine spray of insane acidulated water is used-on the vshale at the Atop of the apparatus,`there also enters at or nearthe'top ofthe chamber .1 the'vapor from the distilling retort, as will be presently described, this vapor consisting principally of hydrocarbons just described and having comparatively low boiling point and great capacity as solvents. It should be notedthat 1n addition to the hydrocarbons which go into the chamber' 1 in the formofy vapor, there is -alsopresent various organic acids, such as acetic acid, which give assistance in the breaking of the adsorptive bond between the oil and the shale, and thus render less important the addition'of supplemental acid applications. y `Closures are provided at the top and bottom of the chamber 1 for limit-l ing the passage of 'shale intoand out of a chamber and also for preventing the'escape of the solvent vapors from the chamber while the shale is being treated. Located adjacent the top of the chamber 1 is a conduit 4 leading ofi' from the chamber and designed to provide a passageway for the discharge of gases to a condenser and scrubber, not shown.

Adjacent the base of the chamber 1 there is a conduit for conducting the extracted liquids and condensed vapors to a suitable tank for storage. This conduit is indicated by the numeral 5.- At the'junction of the conduit with the chamber 1 there isprovided suitable-means .for preventing the discharge of the shale material into the lconduit as indicated by a slotted screen 6 and a wire screen of woven material 7 The conduit 5 is provided with a gooseneck Abend to provide a trap and seal as is .the general practice in such apparatus. At the base of the retori-J 1 provision is made for the discharge of the shale into the inclined tubular retort 8 which is provided with a screw conveyer arranged to carry material through the same. This. tubular retort 8 is providedwith a heating device or furnace as indicated by 9 which makes it possible iso-effect the destructive distillation of material conveyed through the tube 8. Thefurnace 9 may obtain its source of vfuel by any means asis i shown at 10 as an oil or gas heater. At the end of the tube Spfarthermost from the chamber 1 isa discharge passage for the spent shale indicated by 11. At the opposite end from the discharge passage 11 and somewhat nearer the chamber 1,'the tube 8 is provided with a discharge passage 12 for the vapors extracted from ,the shale in the tube 8. These vapors are carried from the tube 8, through the `discharge passage 12 and into a passageway 13 from which they are conducted as vapors to the top of the chamber 1 by means of th'e conduit 14 as will be further described. Heavy matters such as tar which may be liberated in the tube 8 and passed through the discharge passage 12 and passageway 13 may bewere trapped adjacent the bot-tom of the meme'. ber 13I and led to a receiving tank for .tar as indicated bythe passageway r15. op-

-tional'treatment is provlded bythe conduit .diagrammatically at 18,'a' superheater therefor at 19 and a pressure gage at 20.

Inzothefoperation of the process and the apparatus an amount of shale is introduced from the chamber l into the tubular retort 8 where it is subjected to a temperautre nec# essary to drive out all 'volatile matter,'this being effected by the heat of the furnace 9. The volatile matter is then delivered .in the form of a 4vapor or a vapor and liquid through the passageways-12, lsand 14, into the chamber 1 containlng the cold "shale to be treated. The hot vapors condense to 'a certain extent in the chamber of' cold. shale and the hot condensed liquids Aexert the` maximum-'solvent action possible and there'- by take out of the shale a large proportion of thevolatile materials contained therein.` The resulting extracted liquid lcontaining the material previously adsorbed' ,to the shale particles -is drawn off from the chamber l by the -conduit 5. The shale which has v been deprived of its volatile matter is deliyered from the chamber 1 linto the Atube 8 and lconveyed by means of the screw conveyer into that portion of the tube heated by the furnace 9. Here the remaining volai tile matter is extracted by destructive distillationand the resulting vapors containing phenols, pyridine and acids are continually delivered through the passageways 12,13

and 14 into the topof'the chamber1fasjpreviously described Wherethese vapors, -exer' cise their solvent actlon on new portlons of the shale which may beledintothechamber'l. The present application is acontinuation in part of the applicationl filed Dec. l, 1916, now Patent No. 1,244,840, `issued October, 191

From tho foagoing iowiu'bo obvious. that l oils' and other hydrocarbon products by the` land coals which comprises subjecting a mass of such shale or coal containing the desired hydrocarbon matter in acontainer lto the solvent action lofmaterial to which an acid hase-been added, permlttmg the solvent ma-v from by vterial to pass through the mass of sha1-eroi;v

r andrextracted matter. 2. The process of extracting hydrocarbon o1l 'matter from petroleum bearing shales and coals which comprises subjecting the material to betreated to the solvent action of a 'solvent medium to which anacid has 'been added" to removei the hydrocarbon oil material from the shale and break down the adsorptive bond vbetween theoil material and the shale, andv separating the combined solvent medium `and vacid with the material coalfand.' recovering the combined solvent dissolved therebyfrom the shale and coal.

3. The

1 process offextracting 'hydrocarbon o14 matter from Alrt'such shale or coal containing the desired solvent action of mineral acid, rial to pass'through the mass of shale or coal, and recovering the 'combined' solvent andextracted matter. l l The process of treating shalesor'coals toe'xtracthydrocarbon material therefrom .material containing a petroleum bearing shales and coals which comprises su'bjecti'l'igv a mass yirocarbon matter 1n a container to the permitting the `solvent. matewhich comprises the extraction in one cham.

ber of a material` containing `acids from said shale or coalby the destructive dis-A tillation of a portion lof semi-spent shalel or coal, the application ina second chamber of the hot extracted material to a mass of subv stantially untreated shalewhereby said hot extracted material containing acids dissolves hydrocarbon matter from said shale,'and the recovery of the combined solvent and extracted matter in liquid form from said mass of semi-spent shale or coal. 5.- The continuous process of treating shales or coals to extract hydrocarbon "ma, terial therefrom which comprises first the,-

ingfacidsfrom' said shale or coal by the de-lo structive distillation of aportion ofv semif spentshale or coal;the application -in a sec-, fond chamber of the hot extracted material to 'a mass of substantially untreated material whereby said hot extracted material containing acids condenses and dissolves hydrocarbon matter .from said untreated material, the recovery ofthe combined condensed solvent and extracted matter in liquid form this process provides for the-l obtaining of extraction in one chamber of vapor contain-l o from said ,mass of untreated material which thereby becomes semi-spent material, and the subsequent prlmary treatment of said semi-spent material to obtain vapors there-v solvent action of material containing an acidtaken from said shales and coals, permitting destructive distillation in said first t ough the mass ofshale `or coal, and

the;j solvent matter to pass dovvnvvardly rec vering the combined solvent and extracted atter... f

7 The process of extracting hydrocarbon matter from shales and coals which comprises subjecting a mass of suclrfshale or coal 4 containing the desired hydrocarbon matter in a container to the action of hotvaporous material containing acid, condensin said vaporous material in said shale or coa permitting `the condensed materials to pass 4.downwardlythrough the mass of shale or mass of shale or coal Iwhereb ter from said shale, and the recovery of the combined solvent and extracted mattervin liquid form from said mass of semi-spent shale or coal.

9. The process of treating shales or coals to extract lhydrocarbon material therefrom which comprises the extraction in onechamber of solvent material from said shale orv coal by the destructive distillation of a portion of semi-spent shale or coal in the presence of an acid solvent, the' application in a second chamber of the hot extracted material to a mass of Asubstantially untreated shale whereby said hot extracted material dissolves hydrocarbon matter from said shale, and the recovery of thecombined solvent and extracted matter in liquid form from said mass of semi-spent shale or coal.

, maarre,

-shale's r` coals to extract hydrocarbon masaid shale or coal bythe destructive distillation of a portion of semi-spent shale orcoal,

ghe continuous 'process 'of trating terial therefrom which comprises first the y extraction 1n one chamber Iof agvapor from terial condenses and dissolves hydrocarbon matter from said untreated material, the recovery of the combined condensed solvent and extracted matter in liquid form from said mass of untreated material which thereby becomes semi-spent material, and the subsequent primary treatment of said semispent material to obtain vapors therefrom by destructive distillation.

11. The continuous process of treating shales or coals to extract hydrocarbon material therefrom which comprises first. the extraction in one chamber of a vapor from said shale or coal by the destructive distillation of a portion of semi-spent shale or coal, the application in a second chamber of the hot extracted vaporous material to a mass of substantially untreated material in the presence of an acid solvent whereby said hot extracted material condenses` and dissolves hydrocarbon matter from said untreated material, the recovery of the combined condensed solvent and extracted'matter in liquid form from said mass of untreated material which thereby becomes semi-spent material, and the subsequent primar treatment of said semi-spent material to o tain vapors therefrom by destructive distillation.

In testimony whereof I have hereunto set -my hand.

DAVID T. DAY. 

